US4795588A - Method of preparing a luminescent Eu2 + activated strontium aluminate - Google Patents

Method of preparing a luminescent Eu2 + activated strontium aluminate Download PDF

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US4795588A
US4795588A US07/174,554 US17455488A US4795588A US 4795588 A US4795588 A US 4795588A US 17455488 A US17455488 A US 17455488A US 4795588 A US4795588 A US 4795588A
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flux
heat treatment
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Robert J. Pet
Martin M. C. I. van den Nieuwenhof
Josephus P. H. M. Duisters
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US Philips Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734—Aluminates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/44—Devices characterised by the luminescent material

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  • the invention relates to a method of preparing a luminescent Eu 2+ activated strontium aluminate defined by the formula Sr 4 Al 14 O 25 :Eu 2+ , in which a mixture comprising SrO, Al 2 O 3 and Eu 2 O 3 or compounds yielding these oxides upon an increase of temperature is heated in a weakly reducing atmosphere at a temperature of 1100° to 1500° C., and in which a flux is added to the mixture.
  • the invention also relates to a luminescent strontium aluminate obtained in accordance with said method and to a low-pressure mercury vapour discharge lamp provided with a luminescent screen comprising such a luminescent strontium aluminate.
  • Luminescent aluminates defined by the formula Sr 4 Al 14 O 25 :Eu 2+ with an Eu-content of 0.1 to 10 mol % with respect to the Sr present, are known from Netherlands Patent Application 8201943. These aluminates are crystalline compounds having a characteristic X-ray powder diagram which is shown in the said Netherlands Patent Application. Although these aluminates can be obtained by starting from Sr/Al ratios of 1/2 to 1/5, it is assumed that the crystal phase substantially has the composition Sr 4 Al 14 O 25 .
  • the said Netherlands Patent Application describes a method of preparation in which the aluminate is formed by a solid state reaction at a high temperature of a mixture comprising SrO, Al 2 O 3 and Eu 2 O 3 .
  • the use of a flux or melting salt is very desirable.
  • the fluxes H 3 BO 3 , B 2 O 3 and SrF 2 are mentioned as examples.
  • the product obtained can be washed with water in order to remove the greater part of the flux residues present.
  • the final product obtained in accordance with the known method still comprises small quantities of flux residues after washing.
  • the presence of these residues may have a detrimental influence on the Eu 2+ emission. It also appears to be difficult to obtain the desired crystal phase free from disturbing side-phases.
  • a great drawback of the known method is that the aluminate obtained is poorly crystallized and has an unfavourable grain size and grain size distribution so that the luminous flux obtained is not optimum.
  • the aluminate may comprise small quantities of barium (up to at most 10 mol %).
  • the presence of such small quantities of barium does not, however, yield any advantages and is generally found to decrease the efficiency.
  • An object of the invention is to provide a method of preparing luminescent strontium aluminate defined by the formula Sr 4 Al 14 O 25 :Eu 2+ in such a way that the desired crystal lattice of the aluminate is formed very satisfactorily so that the aluminates have a very efficient Eu 2+ emission.
  • a method of preparing a luminescent Eu 2+ activated strontium aluminates defined by the formula Sr 4 Al 14 O 25 :Eu 2+ as described in the opening paragraph is characterized in that: per mol of the Al present, a combination of between 0.1 and 5 mol % of B 2 O 3 or compounds yielding B 2 O 3 upon an increase of temperature, and between 0.1 and 10 mol % of at least one of the fluorides and/or chlorides of Ba, Sr, Cs and/or Al and/or RbCl is added to the mixture as a flux; whereafter the mixture is subjected to a first heat treatment at 1100° to 1500° C.; per mol of the Al present, between 0.1 and 10 mol % of at least one of the ammonium halogenides is added as a flux to the product thus obtained; and the mixture thus obtained is subsequently subjected to a second heat treatment at a temperature of 700° to 1200° C.
  • At least one of the ammonium halogenides is added to the product obtained after the first heat treatment and subsequently the mixture thus obtained is heated for a second time.
  • This second heat treatment does not substantially change the luminescence properties of the aluminate powder obtained.
  • the second heat treatment is, however, necessary if the luminescent aluminate is to be used in low-pressure mercury vapour discharge lamps. In fact, due to the second heat treatment, a great improvement in the luminous flux is then obtained and the luminous flux is maintained during the lifetime of the lamps. If less than the stated quantity of NH 4 halogenides is added during the second heat treatment, the effect of the second heat treatment is insufficient.
  • a quantity which is larger than the stated maximum quantity does not result in any improvement and has practical drawbacks.
  • a small quantity of the metal elements originating from the fluxes used is always left in the luminescent aluminate, regardless of the quantity of fluxes used.
  • B 2 O 3 and/or H 3 BO 3 in combination with BaF 2 is used as a flux in the first heat treatment.
  • the Ba is at least partly removed as BaFCl due to the addition of NH 4 Cl during the second heat treatment.
  • the Eu 2+ activated strontium aluminate obtained by the method according to the invention is very suitable for use in a low-pressure mercury vapour discharge lamp.
  • the aluminate is very well excited by the mercury resonance radiation (approximately 254 nm) generated in this lamp.
  • the drawing is a diagrammatic cross-section of a low-pressure mercury vapour discharge lamp.
  • a low-pressure mcercury vapour discharge lamp has a tubular glass wall 1.
  • Electrodes 2 and 3 between which the discharge is maintained during operation are placed at the ends of the lamp.
  • the lamp contains a small quantity of mercury and a rare gas as a starter gas.
  • the wall 1 constitutes a luminescent screen and serves as a support for the luminescent layer 4 comprising an Eu 2+ activated strontium aluminate obtained by the method according to the invention.
  • the layer 4 may be conventionally provided on the wall 1, for example, by means of a suspension comprising the luminescent material.
  • This mixture was heated in a furnace at 1350° C. for 2 hours in a weakly reducing atmosphere.
  • This atmosphere was obtained by passing a nitrogen flow (15 liters/min) comprising 6 vol % of H 2 first through water of 24° C. and subsequently into the furnace.
  • the product thus obtained was mixed with 7.0 g of NH 4 Cl (1.5 mol % with respect to Al).
  • This mixture was subsequently heated for 1 hour at 1000° C. in such a reducing atmosphere.
  • the product obtained was then washed in heated diluted HNO 3 (70° C.) in order to remove the remaining flux residues as much as possible.
  • a quantum efficiency Q of 91.3% upon excitation by 254 nm radiation was measured on the final product thus obtained.
  • the absorption A of the exciting radiation was 92.0%.
  • the location of the emission maximum ⁇ max was 492 nm.
  • Example 1 In order to determine the influence of the halogen chosen in the ammonium halogenide, four strontium aluminates were prepared analogously to Example 1 in which in addition to NH 4 Cl also the ammonium halogenides NH 4 F, NH 4 Br and NH 4 I were used during the second heat treatment.
  • Table 1 Examples 2 to 5, shows the ammonium halogenide NH 4 X used during the second heat treatment, the quantity of ammonium halogenide in mol % per mol of the Al present, the quantum efficiency Q in % and the absorption A in % at 254 nm radiation and the location of the emission maximum ⁇ max in nm.
  • Low-pressure mercury vapour discharge lamps of the TLD 36 W type were made of the strontium aluminate obtained by the method according to Example 1. Furthermore low-pressure mercury vapour discharge lamps of the same type were also made for the purpose of comparison, starting from two strontium aluminates a and b obtained by methods not according to the invention.
  • the aluminates a and b were prepared without using a second heat treatment with ammonium halogenide.
  • the aluminate a was obtained by using BaF 2 together with H 3 BO 3 as a flux during a heat treatment analogous to the first heat treatment as described in example 1.
  • the quantum efficiency of this aluminate a was 88.2% and the absorption was 90.9%.
  • the aluminate b was obtained in the same way as aluminate a by using AlF 3 instead of BaF 2 during the first heat treatment.
  • the quantum efficiency of this aluminate b was only 78.7% and the absorption was 90.7%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

Method of preparing a luminescent Eu2+ activated strontium aluminate defined by the formula Sr4 Al14 O25 :Eu2+ in which per mol of the Al present a combination of between 0.1 and 5 mol % of B2 O3 or compounds yielding B2 O3 upon an increase of temperature, and between 0.1 and 10 mol % of at least one of the fluorides and/or chlorides of Ba, Sr, Cs and/or Al and/or RbCl as a flux to a mixture comprising SrO, Al2 O3 and Eu2 O3 or compounds yielding these oxides upon an increase of temperature, whereafter the mixture is subjected to a first heat treatment in a weekly reducing atmosphere at 1100° to 1500° C. Between 0.1 and 10 mol % of at least one of the ammonium halogenides is added per mol of the Al present to the product thus obtained, and the mixture thus obtained is subsequently subjected to a second heat treatment at a temperature of 700° to 1200° C.

Description

BACKGROUND OF THE INVENTION
The invention relates to a method of preparing a luminescent Eu2+ activated strontium aluminate defined by the formula Sr4 Al14 O25 :Eu2+, in which a mixture comprising SrO, Al2 O3 and Eu2 O3 or compounds yielding these oxides upon an increase of temperature is heated in a weakly reducing atmosphere at a temperature of 1100° to 1500° C., and in which a flux is added to the mixture. The invention also relates to a luminescent strontium aluminate obtained in accordance with said method and to a low-pressure mercury vapour discharge lamp provided with a luminescent screen comprising such a luminescent strontium aluminate.
Luminescent aluminates defined by the formula Sr4 Al14 O25 :Eu2+ with an Eu-content of 0.1 to 10 mol % with respect to the Sr present, are known from Netherlands Patent Application 8201943. These aluminates are crystalline compounds having a characteristic X-ray powder diagram which is shown in the said Netherlands Patent Application. Although these aluminates can be obtained by starting from Sr/Al ratios of 1/2 to 1/5, it is assumed that the crystal phase substantially has the composition Sr4 Al14 O25. The said Netherlands Patent Application describes a method of preparation in which the aluminate is formed by a solid state reaction at a high temperature of a mixture comprising SrO, Al2 O3 and Eu2 O3. In this method the use of a flux or melting salt is very desirable. The fluxes H3 BO3, B2 O3 and SrF2 are mentioned as examples. After cooling, the product obtained can be washed with water in order to remove the greater part of the flux residues present.
The final product obtained in accordance with the known method still comprises small quantities of flux residues after washing. The presence of these residues may have a detrimental influence on the Eu2+ emission. It also appears to be difficult to obtain the desired crystal phase free from disturbing side-phases. A great drawback of the known method is that the aluminate obtained is poorly crystallized and has an unfavourable grain size and grain size distribution so that the luminous flux obtained is not optimum.
The said Netherlands Patent Application states that the aluminate may comprise small quantities of barium (up to at most 10 mol %). The presence of such small quantities of barium does not, however, yield any advantages and is generally found to decrease the efficiency.
An object of the invention is to provide a method of preparing luminescent strontium aluminate defined by the formula Sr4 Al14 O25 :Eu2+ in such a way that the desired crystal lattice of the aluminate is formed very satisfactorily so that the aluminates have a very efficient Eu2+ emission.
SUMMARY OF THE INVENTION
According to the invention a method of preparing a luminescent Eu2+ activated strontium aluminates defined by the formula Sr4 Al14 O25 :Eu2+ as described in the opening paragraph is characterized in that: per mol of the Al present, a combination of between 0.1 and 5 mol % of B2 O3 or compounds yielding B2 O3 upon an increase of temperature, and between 0.1 and 10 mol % of at least one of the fluorides and/or chlorides of Ba, Sr, Cs and/or Al and/or RbCl is added to the mixture as a flux; whereafter the mixture is subjected to a first heat treatment at 1100° to 1500° C.; per mol of the Al present, between 0.1 and 10 mol % of at least one of the ammonium halogenides is added as a flux to the product thus obtained; and the mixture thus obtained is subsequently subjected to a second heat treatment at a temperature of 700° to 1200° C.
Experiments which have led to the invention have proved that the desired crystal lattice of Sr4 Al14 O25 :Eu2+ is very satisfactorily formed if in a first heat treatment at 1100° to 1500° C. both B2 O3 and also at least one of the fluorides and/or chlorides of Ba, Sr, Cs and/or Al and/or RbCl is used as a flux in the mixture of oxides. If more than the flux quantities stated are used, too many unwanted compounds are formed as side-phases. However, if fewer than the quantities stated are used, an insufficient flux effect will occur so that the desired crystal phase is incompletely formed. At least one of the ammonium halogenides is added to the product obtained after the first heat treatment and subsequently the mixture thus obtained is heated for a second time. In this second heat treatment, possible flux residues are at least partly removed. This second heat treatment does not substantially change the luminescence properties of the aluminate powder obtained. The second heat treatment is, however, necessary if the luminescent aluminate is to be used in low-pressure mercury vapour discharge lamps. In fact, due to the second heat treatment, a great improvement in the luminous flux is then obtained and the luminous flux is maintained during the lifetime of the lamps. If less than the stated quantity of NH4 halogenides is added during the second heat treatment, the effect of the second heat treatment is insufficient. A quantity which is larger than the stated maximum quantity does not result in any improvement and has practical drawbacks. In practice, a small quantity of the metal elements originating from the fluxes used is always left in the luminescent aluminate, regardless of the quantity of fluxes used.
In a preferred embodiment of the method according to the invention, B2 O3 and/or H3 BO3 in combination with BaF2 is used as a flux in the first heat treatment.
With this combination of B2 O3 and BaF2 as a flux during the first heat treatment, the best results as regards crystal formation are obtained. The Ba is at least partly removed as BaFCl due to the addition of NH4 Cl during the second heat treatment.
The Eu2+ activated strontium aluminate obtained by the method according to the invention is very suitable for use in a low-pressure mercury vapour discharge lamp. The aluminate is very well excited by the mercury resonance radiation (approximately 254 nm) generated in this lamp.
BRIEF DESCRIPTION OF THE DRAWING
Embodiments of the method according to the invention will now be described in greater detail by way of example with reference to the accompanying drawing.
The drawing is a diagrammatic cross-section of a low-pressure mercury vapour discharge lamp.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawing, a low-pressure mcercury vapour discharge lamp has a tubular glass wall 1.
Electrodes 2 and 3 between which the discharge is maintained during operation are placed at the ends of the lamp. The lamp contains a small quantity of mercury and a rare gas as a starter gas. The wall 1 constitutes a luminescent screen and serves as a support for the luminescent layer 4 comprising an Eu2+ activated strontium aluminate obtained by the method according to the invention. The layer 4 may be conventionally provided on the wall 1, for example, by means of a suspension comprising the luminescent material.
EXAMPLE 1
A mixture was made of
354.10 g of SrCO3
432.14 g of Al2 O3
10.66 g of Eu2 O3
7.48 g of H3 BO3 (0.7 mol % of B2 O3 with respect to Al)
20.62 g of BaF2.
This mixture was heated in a furnace at 1350° C. for 2 hours in a weakly reducing atmosphere. This atmosphere was obtained by passing a nitrogen flow (15 liters/min) comprising 6 vol % of H2 first through water of 24° C. and subsequently into the furnace. The product thus obtained was mixed with 7.0 g of NH4 Cl (1.5 mol % with respect to Al). This mixture was subsequently heated for 1 hour at 1000° C. in such a reducing atmosphere. The product obtained was then washed in heated diluted HNO3 (70° C.) in order to remove the remaining flux residues as much as possible. A quantum efficiency Q of 91.3% upon excitation by 254 nm radiation was measured on the final product thus obtained. The absorption A of the exciting radiation was 92.0%. The location of the emission maximum λmax was 492 nm.
EXAMPLES 2 TO 5
In order to determine the influence of the halogen chosen in the ammonium halogenide, four strontium aluminates were prepared analogously to Example 1 in which in addition to NH4 Cl also the ammonium halogenides NH4 F, NH4 Br and NH4 I were used during the second heat treatment. Table 1, Examples 2 to 5, shows the ammonium halogenide NH4 X used during the second heat treatment, the quantity of ammonium halogenide in mol % per mol of the Al present, the quantum efficiency Q in % and the absorption A in % at 254 nm radiation and the location of the emission maximum λmax in nm.
              TABLE 1                                                     
______________________________________                                    
ex. NH.sub.4 X                                                            
             quantity (mol %)                                             
                          Q (%)  A (%) λ.sub.max                   
______________________________________                                    
                                       (nm)                               
2   NH.sub.4 CL                                                           
             3.8          84.2   91.7  492                                
3   NH.sub.4 F                                                            
             5.4          84.2   92.4  493                                
4   NH.sub.4 Br                                                           
             2.1          84.1   91.8  493                                
5   NH.sub.4 I                                                            
             1.4          82.9   91.8  494                                
______________________________________
EXAMPLES 6 TO 13
In a manner corresponding to Example 1 strontium aluminates were obtained in which not only BaF2 but also the salts BaCl2, CsF, CsCl, SrF2, SrCl2, AlF3, AlCl3 and RbCl were used as fluxes during a first heat treatment. The second heat treatment took place in all eight cases after addition of NH4 Cl. Table 2, Examples 2 and 6 to 13, shows the fluxes used during the first heat treatment, the quantity of flux in mol % per mol of the Al present Q, A and λmax.
              TABLE 2                                                     
______________________________________                                    
ex.  flux    quantity (mol %)                                             
                          Q (%)  A (%) λ.sub.max                   
______________________________________                                    
                                       (nm)                               
2    BaF.sub.2                                                            
             1.3          84.2   91.7  492                                
6    BaCl.sub.2                                                           
             1.1          87.0   91.9  494                                
7    CsF     1.4          83.9   91.9  493                                
8    CsCl    1.2          84.9   87.8  495                                
9    SrF.sub.2                                                            
             1.6          87.7   89.3  489                                
10   SrCl.sub.2                                                           
             1.3          85.3   89.4  494                                
11   AlF.sub.3 *                                                          
             1.5          78.9   91.1  494                                
12   AlCl.sub.3                                                           
             1.5          85.4   90.8  488                                
13   RbCl    1.7          79.6   87.3  495                                
______________________________________                                    
 *AlF.sub.3 was added as AlF.sub.3.3H.sub.2 O.
EXAMPLES 14 TO 18
Analogously to the method of Example 1 strontium aluminates were prepared in which use was made of different quantities of the salts BaF2 and CsF during a first heat treatment. Table 3 shows the salt used, the quantity of these salts in mol % per mol of the Al present, Q and A.
              TABLE 3                                                     
______________________________________                                    
ex.    flux   quantity (mol %)                                            
                              Q (%) A (%)                                 
______________________________________                                    
14     BaF.sub.2                                                          
              1.3             92.5  88.8                                  
15     BaF.sub.2                                                          
              2.6             90.8  91.7                                  
16     CsF    0.6             87.3  85.9                                  
17     CsF    2.0             88.4  90.8                                  
18     CsF    5.6             82.4  94.4                                  
______________________________________
Low-pressure mercury vapour discharge lamps of the TLD 36 W type were made of the strontium aluminate obtained by the method according to Example 1. Furthermore low-pressure mercury vapour discharge lamps of the same type were also made for the purpose of comparison, starting from two strontium aluminates a and b obtained by methods not according to the invention. The aluminates a and b were prepared without using a second heat treatment with ammonium halogenide. The aluminate a was obtained by using BaF2 together with H3 BO3 as a flux during a heat treatment analogous to the first heat treatment as described in example 1. The quantum efficiency of this aluminate a was 88.2% and the absorption was 90.9%. The aluminate b was obtained in the same way as aluminate a by using AlF3 instead of BaF2 during the first heat treatment. The quantum efficiency of this aluminate b was only 78.7% and the absorption was 90.7%. Table 4 shows the initial light output and the light output after 100 operating hours of the lamps. The initial light output is given in lm/W and in % with respect to the light output after 100 operating hours. The light output after 100 operating hours (=100%) is given in lm/W. This Table shows that a second heat treatment with the addition of ammonium halogenide in the preparation of the strontium aluminate leads to luminescent aluminates having a better lamp behaviour (initial light output and maintenance of the light output during operation of the lamp) than the luminescent aluminates obtained without such a second heat treatment.
              TABLE 4                                                     
______________________________________                                    
Light output after 0 hr in                                                
                     light output after                                   
ex.   1 m/W        %         100 hrs in 1 m/W                             
______________________________________                                    
1     84.3         101.7     82.9                                         
a     81.5         103.2     79.1                                         
b     77.2         103.0     74.9                                         
______________________________________

Claims (2)

What is claimed is
1. A method of preparing a luminescent Eu2+ activated strontium aluminate defined by the formula Sr4 Al14 O25 :Eu2+, in which a mixture comprising SrO, Al2 O3, Eu2 O3 or compounds yielding these oxides at the heating temperature employed and a flux is heated in a weakly reducing atmosphere at a temperature of 1100° to 1500° C.,
characterized in that: per mol of the Al present, a combination of between 0.1 and 5 mol % of B2 O3 or compounds yielding B2 O3 at said heating temperature and between 0.1 and 10 mol % of at least one of the fluorides and/or chlorides of Ba, Sr, Cs and/or Al and/or RbCl is present as the flux; whereafter; per mol of the Al present, between 0.1 and 10 mol % of at least one ammonium halide is added as a flux to the so heated mixture; and the mixture thus obtained is subsequently heated at a temperature of 700° to 1200° C. to effect at least partial removal of flux residues present.
2. A method as claimed in claim 1, in which B2 O3 and/or H3 BO3 in combination with BaF2 are used as the flux in the first heating.
US07/174,554 1987-04-07 1988-03-29 Method of preparing a luminescent Eu2 + activated strontium aluminate Expired - Fee Related US4795588A (en)

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NL8700808 1987-04-07
NL8700808A NL8700808A (en) 1987-04-07 1987-04-07 METHOD FOR PREPARING A LUMINESCENT EU2-ACTIVATED STRONTIUM ALUMINATE, ALUMINATED IN SUCH A WAY AND LOW-PRESSURE VAPOR DISCHARGE LAMP INCLUDING SUCH AN ALUMINATE

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US5879586A (en) * 1995-09-29 1999-03-09 Matsushita Electric Industrial Co., Ltd. Method for producing aluminate phosphor
US6660186B2 (en) 2001-10-31 2003-12-09 Matsushita Electric Industrial Co., Ltd. Method of making blue emitting aluminate phosphor for VUV excited light emitting device
US20040135122A1 (en) * 2002-11-22 2004-07-15 Hyland Robert W. Photoluminescent alkaline earth aluminate and method for making the same
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US20040135122A1 (en) * 2002-11-22 2004-07-15 Hyland Robert W. Photoluminescent alkaline earth aluminate and method for making the same
CN100381618C (en) * 2006-08-30 2008-04-16 大连理工大学 A method for preparing aluminate long afterglow luminescent plate
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US9536725B2 (en) 2013-02-05 2017-01-03 Clemson University Means of introducing an analyte into liquid sampling atmospheric pressure glow discharge
US10269525B2 (en) 2013-02-05 2019-04-23 Clemson University Research Foundation Means of introducing an analyte into liquid sampling atmospheric pressure glow discharge
US10533996B2 (en) 2013-08-19 2020-01-14 University Of Houston Phosphorescent reporters
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JP2661952B2 (en) 1997-10-08
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DE3863222D1 (en) 1991-07-18
JPS63265990A (en) 1988-11-02
EP0286180B1 (en) 1991-06-12

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